Compositions containing collagen products and applications thereof



Patented Apr. 26, 1938 UNITE COMPOSITIONS CONTAINING CQLLAGEN PRODUCTS AND APPLICATIGNS THERE- F Wilfred Graham Dewsbury, London, and Arnold Davies. .West Norwood, London, England Claims.

5 whether of animal or marine origin is heated in such non-aqueous organic liquids as mineral or animal or vegetable oils having a boiling point of not lower than 130 C. for a sufllclent period of time at a temperature of approximately 130 C., a mass of tangled collagen fibres separates from the glue or gelatin,'which fibres are insoluble in the organic liquid at the said temperature, leaving a phase of the glue or gelatin dissolved or dispersed in the organic liquid and capable of removal from the fibresby simple decantatlon with washingof the fibres with a little of the liquid.

The present invention is based on the discovery that when the said collagen fibres are separated and freed from adherent 011 they are easily dispersed in water with the production of a dispersion which has many valuable properties as will be hereinafter described.

This dispersion is physically diiierent from the products of swelling of gelatin or glue in water. Ordinary gelatin has known gelation properties for instance 2% yields a firm gel in water. However, the collagen fibres have much smaller gelation factors and it requires considerably larger proportions by weight of fibres to efiect similar gelation.

Torsion viscometry readings indicate that a 1% dispersion of collagen fibres from gelatin, obtained by this present process, in water at room temperature (15 0.), gives a gel of 30% lower viscosity than a similar dispersion of 1% commercial gelatin in water at like temperature,

It is also found that 5% of the collagen fibres from glue obtained by this process, when dispersed in water at room temperature (15 0.), gives a viscosity ascertained by torsion viscometry of one thirteenth of the viscosity of 5% of ordinary good grade commercial glue when dispersed in water at the same temperature.

It is known that very dilute solutions (1.0%) of pure gelatin would gel at low temperatures (10 C.) but that above certain temperatures, approximately 30-35 C., gelation would not take place at any concentration. We find that in similar dispersions of gelatin fibres obtained by this process there is evidence of a continuance of the gel system which affords a plastic physical factor dependent on the concentration of the dispersion.

We find that torsion viscometry readings indicate a fair-stability of viscosity when dispersions of glue and gelatin fibres are subjected to repeated variations of temperature.

Again, whenever glue is used at such concentrations that a jelly results upon cooling to room temperature, it must be handled with alacrity to obtain the full value of its adhesive property. We find that the rate of setting of the glue can be retarded by a difiusion of collagen fibres from glue into ordinary commercial glue to enable adequate penetration of the pores of the material to which the adhesive is applied, without seriously diminishing the adhesive strength of the glue.

This is of particular importance in such cases as in the fixation of cardboard, paper and artificial leather to wood or metal, when the strength necessary is only that of the paper or cardrd.

Such diffusion of fibres exercises a plasticizing effeet on the glue.

The amount of glue fibres or gelatin fibres yielding the best plasticizing values for adhesive and sizing purposes depends on the viscosity of glues normally used in industrial practice. Broadly a dispersion of 10% weight/volume of glue fibres in a 50% normal hide glue product is a guide to the consistency which retards gelling at room temperature.

In the refrigeration of gelatin dispersions in water it is known that the "bound water cannot be frozen and is presumably in union with gelatin molecules.

We have found in comparative dilatorneter readings between depressing temperatures of similar concentrations of commercial gelatin and gelatin fibres that in the case of gelatin there is no indication of expansion until a temperature of 0 C. has been held for some time, when a sudden expansion takes place with the formation of ice crystals. On the other hand similar capillary readings on similar concentrations of our gelatin fibres through similar depressions of temperature indicate a gradual expansion of the gel.

This is of importance in ice cream industry technique. After the frozen cream has been al-- lowed to stand for a day or two it will be found that the water which is present to the extent of 60% to 70% will begin to crystallize out in the crystals without the corresponding disadvantage of the culinary desert gel which similar amounts of gelatin would produce. e

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2 amnesia A 2% dispersion of gelatin fibres obtained from an edible oil treatment in the water used for ice cream manufacture serves as an eficient stabilizer for the fatty products and yields a product having a smooth texture without the undue gel ling effect of gelatin.

Again, it has been found that the product of fibre dispersion in water has little or none of the adhesiveness, stiffness or elasticity characteristic of aqueous glue.

It is well known that the operation oi dry grinding of most substances below say 200 mesh is difiicult. As subdivision proceeds the total free surface increases enormously and apart from the inherent difliculty of breaking up a very fine particle the tendency of the fragments to reunite or cake-up begins to assert itself.

The finer the particles the greater this tendency and it is increased by pressure.

' It is well known that these difliculties are partially overcome by wet grinding.

In accordance with the present invention a dispersion of collagen fibres in the water of grinding becomes adsorbed at the new'surfaces, and tends to de-fiocculate the powder, preventing the reunion of the particles. This is particularly noticeable with such materials as graphite, sulphur.

' zinc oxide and the like.

A 2% dispersion of glue fibres in the water of wetting out" serves to defiocculate the materials, and thus assists the presentation of fresh surfaces to the grinding mechanism.

The commercial advantages oi such defioccuiated materials are important. In the case of graphite, a defiocculated graphite suspension in water is more efiective for the impregnation oi fibre materials, for instance as in electrical resistances. In the case of sulphur, a dispersion of colloidal particle size is important in vulcanization ,of rubber processes, while we find that the 'dispersion of collagen fibres in water provides a protective colloid enabling asbestos to be added to latex without the disadvantage of coagulation of the rubber.

In relation to a further feature of the invention it is well known that stable emulsions of two pure liquids cannot be made, and that it is necessary to employ a third substance to stabilize the emulsion.

It is also well known that gelatin and glue are useful stabilizers for emulsions of oils in water.

According to this invention the use of a dispersion of collagen fibres as a stabilizing agent is of particular advantage. For instance in the case of oil-in-water emulsions, the viscosities do not increase considerably when the volume 01 the disperse phase increases. This is important for instance in the commercial use of emulsions oi oil and water containing pigments commonly known as water distempers. In such emulsions the dispersion of collagen fibres has the effect of wetting out and subdividing the inert pigments.

For example, torsion viscometry readings when 1% gelatin is used as a stabilizer to promote a 50% oil in water emulsion with commercial boiled"-linseed oil indicate an increase in viscosity of 83% as compared with the similar use as a stabilizer of 1% of gelatin fibres dispersed in the water.

Furthermore, 1% of gelatin fibres (obtained by treatment of gelatin according to our process with an edible oil, such as olive oil) dispersed in 50% water is an efiicient stabilizer for 50% olive oil for mayonnaise.

A further advantage in the indust obtaining exactly the correct consistency of glue for this purpose. If the glue is too thin it will penetrate the pores of the cotton fibre to such a degree that the latter will be too stiif to use, while if it is too viscous it will not be absorbed at all, and will fail to dry out during its passage through the drying chamber. We find that a. diffusion oi glue fibres into the normal glue preparation used in such technique plaaticizes the glue to give a better wetting-out" of the cotton fibre without undue stifl'ness.

Moreover, in the case of gelatin fibres, we find that dispersions of about 2% in the juice of fruits as tinned preserves or Jams, or meat extracts, give an appearance of better quality of the product, while a similar addition to cream enables it to be whipped more easily.

' Obviously, whenever gelatin fibres are to be used in food products they must be dispersed according to the manner of our specification in edible oils such as olive oil, peanut oil. etc.

It is, moreover, well known that glue or gelatin is a stabilizer or acts as a protective colloid to prevent the coagulation of the, rubber particles in commercial latex but'ev'en when the diameter of the gelatin or glue particles is further reduced as by homogenization, films of dried latex show distinct separation of glue or gelatin, which has a tendency to-make the product sticky or tacky.

Various proposals have already been made for concentrating rubber latices, especially by evaporation, filtering, centrifuging and creaming, the limits to which the concentration could be carried without coagulation having been substantially extended by the addition of protective colloids, and the stability very much increased. 4

According to a. still further feature of the present invention, when collagen fibres are dispersed in the commercial latex and the product evaporated by well known methods, a concentration is.

produced which is more amenable to dispersion on textile materials and the like, and ensures a more even rate of coagulation.

A 1% dispersionoi either gelatin fibres or glue fibres serves as stabilizer to prevent the coagulation of latex which normally occurs after the evaporation of the ammonia normally used in industry for similar Pu p ses.

These dispersions of glue fibres or gelatin fibres also tend to support the fillers and colloidal sulphur used in normal industrial rubber practice technique.

In the appended claims, the term gelatin is intended to include glue and isinglass.

What we claim is:-

1. Process for the manufacture of improved materials containing a. dispersion of collagen fibres comprising the treatment of gelatin with 2,1 ruse 3. A product comprising an aqueous dispersion of isolated fibrous material consisting of that part of gelatin which is insoluble at 130 C. in an oil boiling above 130 C. and belonging to the class consisting of vegetable, animal and mineral oils.

4. Process for the manufacture of improved materials containing collagen derived material comprising heating to a temperature of about 130 C. an oil with a substance selected from the group consisting of glue and gelatin until a fibrous product is formed from said substance selected from the group consisting of glue and gelatin, separating the fibrous product from the oil and dispersing said fibrous product in an aqueous medium.

5. Process for the manufacture of improved materials containing collagen derived material comprising heating to a temperature of about 130 C. an edible oil with a substance selected from the group consisting of glue and gelatin until a fibrous product is formed from said substance selected from the group consisting of glue and gelatin, separating the fibrous product from the oil and dispersing said fibrous product in an aqueous medium.

WILFRED GRAHAM DEWSBURY. ARNOLD DAVIES. 

